EP0676667B1 - Method of processing photographic light-sensitive material - Google Patents
Method of processing photographic light-sensitive material Download PDFInfo
- Publication number
- EP0676667B1 EP0676667B1 EP95105017A EP95105017A EP0676667B1 EP 0676667 B1 EP0676667 B1 EP 0676667B1 EP 95105017 A EP95105017 A EP 95105017A EP 95105017 A EP95105017 A EP 95105017A EP 0676667 B1 EP0676667 B1 EP 0676667B1
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- European Patent Office
- Prior art keywords
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- developer
- formula
- silver
- substituent
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/061—Hydrazine compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/31—Regeneration; Replenishers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/164—Rapid access processing
Definitions
- the invention relates to a method of processing a silver halide photographic light-sensitive material, and particularly to a method of processing a silver halide photographic light-sensitive material which makes it possible in the rapid processing condition to reduce silver sludge which adheres to developing tanks or racks or rollers and to reduce a replenishing amount of processing solution replenisher.
- a scanner is widely used in the printing plate-making field.
- a light source used in these recording apparatus includes a glow lamp, xenon lamp, tungsten lamp, LED, a He-Ne laser, a argon laser or a semiconductor laser.
- a light sensitive material used in the scanner is required to have various photographic properties. It is essential that the light sensitive material have high sensitivity and high contrast, since short light-exposure time such as 10 -3 to 10 -7 seconds is carried out. In the printing industry high operation efficiency and high operation speed are strongly demanded, and here are needs for increasing a scanning speed and shortening the processing time of the light-sensitive material.
- the increase of the scanning speed, the increase of a beam number and less beam spots for a high image quality are required for an exposure device (a scanner, a plotter), and high sensitivity, excellent stability and rapid processability for a silver halide photographic light-sensitive material.
- the rapid processing referred to herein is a processing in which the total processing time is 15 to 60 seconds.
- the total processing time is a time taken from the entry of the leading edge of a film in the apparatus to the delivery of the leading edge out of the drying zone of the apparatus.
- the film is conveyed through the developing tank, the cross-over, the fixing tank, the cross-over, the washing tank, the cross-over and the drying zone in the automatic developing apparatus.
- EP-A-0 529 526 relates to a method for rapid processing which enables reduced silver stain formation on the walls of developing tanks and reduced replenishment rates by using a developer comprising a heterocyclic ring compound having a mercapto group as substituent on the heterocyclic ring.
- a method for processing a silver halide photographic light-sensitive material which has a rapid processing property and makes it possible to reduce silver sludge and the replenishing amount of replenisher, and to reduce black spots and improve dot quality.
- An object of the invention is to provide a method for processing a silver halide photographic light-sensitive material, which makes it possible in the rapid processing condition to markedly reduce silver sludge and to reduce a replenishing amount of processing solution replenisher.
- Another object of the invention is to provide a method for processing a silver halide photographic light-sensitive material, which makes it possible in the rapid processing condition to improve dot quality and to prevent occurrence of black spots.
- the heterocyclic ring includes an oxazole, benzoxazole, thiazole, benzothiazole, triazine, pyrimidine, tetraazaindolidine, triazaindene or purine ring, and preferably a 5- or 6-membered heterocyclic ring which may be condensed with a benzene ring.
- M represents a hydrogen atom, an alkali metal atom, an alkali earth metal atom or a cation such as an ammonium ion.
- the heterocyclic ring may have a substituent other than -SH, and the substituent includes a halogen atom, a sulfo group, a hydroxy group, a lower alkyl group having 1 to 5 carbon atoms or a phenyl group.
- the compounds represented by Formula (1) preferably have a chemical structure represented by Formula (A) through (C).
- R 1 and R 2 independently represent an alkyl, aryl, aralkyl, hydroxy, carboxy, sulfo, phosphono, amino, nitro, cyano, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfamoyl or alkoxy group or a halogen atom.
- the alkyl, aryl, aralkyl, amino, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfamoyl or alkoxy group may have a further substituent and the substituent includes the same as the group represented by R 1 or R 2 .
- R 1 and R 2 may combine to form a ring.
- R 1 and R 2 preferably represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms, a nitro group, a cyano group or a halogen atom.
- R 1 or R 2 preferably combines to form a saturated 5-membered.
- R 1 more preferably represents a hydrogen atom or an alkyl group having as a substituent an amino group (such as a dimethylamino or diethylamino group) or a heterocyclic ring group (such as a morpholino, N-methylpiperadinyl, pyrrolidinyl or piperidinyl group).
- R 2 more preferably represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.
- R 1 represents dimethylaminomethyl, morpholinomethyl, N-methylpiperadinylmethyl or pyrrolidinylmethyl group.
- R 2 represents a methyl, ethyl, phenyl or p-methoxymethyl group.
- Z 21 and Y 21 independently represent an atomic group necessary to form an unsaturated 5- or 6-membered ring, (such as pyrrole, imidazole, pyrazole, pyrimidine and pyridamine), provided that three or more nitrogen atoms are contained in Z 21 and Y 21 and one of Z 21 and Y 21 has a mercapto group as a substituent.
- an unsaturated 5- or 6-membered ring such as pyrrole, imidazole, pyrazole, pyrimidine and pyridamine
- Compound represented by Formula (B) may have a substituent other than a mercapto group, including, for example, a halogen atom (such as fluorine, chlorine and bromine), a lower alkyl group (including those having a substituent and, preferably, those having not more than 5 carbon atoms such as a methyl group and an ethyl group), a lower alkoxy group (including those having a substituent and, preferably, those having not more than 5 carbon atoms such as methoxy, ethoxy and butoxy), a hydroxy group, a sulfo group, a lower allyl group (including those having a substituent and, preferably, those having not more than 5 carbon atoms), an amino group, a COOM 21 group (in which M 21 represents a hydrogen atom, an alkali-metal atom or an ammonium group), a carbamoyl group and a phenyl group.
- the substituent is particularly preferably a hydroxy group,
- R 21 , R 22 and R 23 independently represent a halogen atom, a lower alkyl group (including those having a substituent and preferably, those having not more than 5 carbon atoms such as a methyl group and an ethyl group), a lower alkoxy group (including those having a substituent and preferably, those having not more than 5 carbon atoms ), a hydroxy group, a sulfo group, a lower allyl group (including those having a substituent and preferably, those having not more than 5 carbon atoms), an amino group, a COOM 21 group (in which M 21 represents the same group as M defined in the above Formula (1)), a carbamoyl group or a phenyl group, provided that one of R 21 , R 22 and R 23 is a mercapto group.
- the group other than a mercapto group is preferably a hydroxy group, a COOM 21 group, an amino group or a sul
- R 21 , R 22 , R 23 and R 24 independently represent a halogen atom, a lower alkyl group (including those having a substituent and preferably, those having not more than 5 carbon atoms such as a methyl group and an ethyl group), a lower alkoxy group (including those having a substituent and preferably, those having not more than 5 carbon atoms ), a hydroxy group, a sulfo group, a lower allyl group (including those having a substituent and preferably, those having not more than 5 carbon atoms), an amino group, a COOM 21 group (in which M 21 represents the same group as M defined in the above Formula (1)), a carbamoyl group or a phenyl group, provided that one of R 21 , R 22 , R 23 and R 24 is a mercapto group.
- the group other than a mercapto group is preferably a hydroxy group, a COOM 21 group,
- R 21 and R 22 independently represent a halogen atom, a lower alkyl group (including those having a substituent and preferably, those having not more than 5 carbon atoms such as a methyl group and an ethyl group), a lower alkoxy group (including those having a substituent and preferably, those having not more than 5 carbon atoms ), a hydroxy group, a sulfo group, a lower allyl group (including those having a substituent and preferably, those having not more than 5 carbon atoms), an amino group, a COOM 21 group (in which M 21 represents the same group as M defined in the above Formula (1)), a carbamoyl group or a phenyl group, provided that one of R 21 and R 22 is a mercapto group.
- the group other than a mercapto group is preferably a hydroxy group, a COOM 21 group, an amino group or a sulfo group.
- R 21 and R 22 independently represent a halogen atom, a lower alkyl group (including those having a substituent and preferably, those having not more than 5 carbon atoms such as a methyl group and an ethyl group), a lower alkoxy group (including those having a substituent and preferably, those having not more than 5 carbon atoms ), a hydroxy group, a sulfo group, a lower allyl group (including those having a substituent and preferably, those having not more than 5 carbon atoms), an amino group, a COOM 21 group (in which M 21 represents the same group as M defined in the above Formula (1)), a carbamoyl group or a phenyl group, provided that one of R 21 and R 22 is a mercapto group.
- the group other than a mercapto group is preferably a hydroxy group, a COOM 21 group, an amino group or a sulfo group.
- R 21 , R 22 , R 23 and R 24 independently represent a halogen atom, a lower alkyl group (including those having a substituent and preferably, those having not more than 5 carbon atoms such as a methyl group and an ethyl group), a lower alkoxy group (including those having a substituent and preferably, those having not more than 5 carbon atoms ), a hydroxy group, a sulfo group, a lower allyl group (including those having a substituent and preferably, those having not more than 5 carbon atoms), an amino group, a COOM 21 group (in which M 21 represents the same group as M defined in the above Formula (1)), a carbamoyl group or a phenyl group, provided that one of R 21 , R 22 and R 23 is a mercapto group.
- the group other than a mercapto group is preferably a hydroxy group, a COOM 21 group, an amino group or
- R 21 , R 22 and R 23 independently represent a hydrogen atom, -SM 21 , a hydroxy group, a lower alkoxy group, -COOM 21 , an amino group, -SO 3 M 23 or a lower alkyl group, provided that one of R 21 , R 22 and R 23 is -SM 21 , wherein M 21 , M 22 and M 23 independently represent a hydrogen atom, an alkali metal atom or an ammonium group and may be the same or different.
- the lower alkoxy or alkyl group represented by R 21 , R 22 and R 23 has a group having 1-5 carbon atoms and preferably 1-3 carbon atoms which may have a substituent.
- the amino group represented by R 21 , R 22 and R 23 represents a substituted or unsubstituted amino group.
- the substituent thereof is preferably a lower alkyl group.
- the ammonium group represents a substituted or unsubstituted ammonium group, and preferably an unsubstituted ammonium group.
- Z 31 and Y 31 independently represent an atomic group necessary to form an unsaturated 5- or 6-membered ring, provided that 3 or more nitrogen atoms are contained in Z 31 and Y 31 and one of Z 31 and Y 31 has a mercapto group as a substituent.
- R 31 , R 32 , R 33 and R 34 independently represent a hydrogen atom, -SM 31 , a hydroxy group, a lower alkoxy group, -COOM 32 , an amino group, -SO 3 M 33 or a lower alkyl group, provided that one of R 31 , R 32 , R 33 and R 34 has a -SM 31 as a substituent wherein M 31 , M 32 and M 33 independently represent a hydrogen atom, an alkali metal atom or an ammonium and may be the same or different.
- the lower alkyl group or lower alkoxy group represented by R 31 , R 32 , R 33 or R 34 has 1 to 5 carbon atoms which may have a substituent, and preferably has 1 to 3 carbon atoms.
- the amino group represented by R 31 , R 32 , R 33 or R 34 represents a substituded or unsubstituded amino group, and preferably represents an amino group having a lower alkyl group.
- Examplified compounds represented by Formulas (g) and (h) will be shown, but not limited thereto.
- Examplified compounds represented by Formula (g) R 31 R 32 R 33 R 34 g-1 -SH H H H g-2 -SH -OH H H g-3 -SH H -OH H g-4 -SH -CH 3 -OH H g-5 -SH -NH 2 H H g-6 -SH H H -NH 2 g-7 -SH H -CH 3 -CH 3 g-8 -SH H H -SH g-9 -SH -OH H -SH g-10 -SH H H -COOH g-11 H -SH H H g-12 -SH -SH H H H g-13 H -SH -OH H g-14 H -SH -NH 2 H g-15 H -SH -OH -CH 3 g-16 H -SH -NH 2 -C 2 H 5 g-17 H -SH H -CH 3
- the content of compounds represented by Formula (1) in the backing layer is preferably 7-150mg/m 2 .
- the content is more preferably 5-200mg/m 2 , most preferably 10-100mg/m 2 , in view of conditions such as reduction of dissolved silver and photographic properties.
- the backing layer herein refers to a layer provided on the support opposite a silver halide emulsion layer and contains a binder such as a hydrophilic binder.
- the thickness of the backing layer is 2 to 7 ⁇ m, and preferably 3 to 5 ⁇ m.
- the compounds represented by Formula (1) is preferably added to an uppermost layer or a layer adjacent to the uppermost layer.
- the replenishing amount of developer replenisher when the replenishing amount of developer replenisher is not more than 200ml/m 2 , it is possible to reduce a dissolving silver amount more than that in the conventional method. Even when the replenishing amount of developer replenisher is not more than 160ml/m 2 or not more than 100ml/m 2 , it is possible to keep a dissolving silver amount to a lesser extent. As a result, the reduction of the replenishing amount of developer replenisher brings about prevention of silver sludge occurrence.
- the replenishing amount of developer replenisher used in the invention is preferably 50 to 160ml/m 2 , and more preferably 70 to 120ml/m 2 .
- the developer replenisher may be the same as or different from developer used, and preferably the same as developer used.
- the photographic light-sensitive material used in the invention preferably contain a contrast increasing agent such as a hydrazine derivative or a tetrazolium compound.
- the light-sensitive material used in the invention contain a hydrazine derivative or a tetrazolium compound dot quality is greatly improved or occurrence of black spots is reduced by addition of the compound represented by Formula (1) to the backing layer.
- A represents an aliphatic group, a cyclic alkyl group having 1 to 20 carbon atoms an aryl group or a heterocyclic group.
- the aliphatic group represented by A is preferably a group having 1 to 30 carbon atoms, and more preferably a straight-chained or branched alkyl group having 1 to 20 carbon atoms.
- the examples thereof include a methyl, ethyl, t-butyl, octyl, cyclohexyl and benzyl group, each of which may have a substituent such as an aryl, alkoxy, aryloxy, alkylthio, arylthio, sulfoxy, sulfonamide, acylamino, or ureido group.
- the aryl group represented by A is preferably a single or condensed ring group, for example, a benzene ring or a naphthalene ring.
- the heterocyclic group represented by A is preferably a single or condensed ring group containing a heterocycle having one hetero atom selected from a nitrogen, sulfur and oxygen atom, such as a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring or a furan ring.
- a nitrogen, sulfur and oxygen atom such as a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring or a
- A especially preferably represents an aryl group or a heterocyclic group.
- the aryl or heterocyclic group of A may have a substituent.
- the substituent include an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a single or condensed ring group having an alkyl group of 1 to 3 carbon atoms), an alkoxy group (preferably having an alkyl group of 1 to 20 carbon atoms), a substituted amino group (preferably having an alkyl group or alkylidene group of 1 to 20 carbon atoms), an acylamino group (preferably having 1 to 40 carbon atoms), a sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 to 40 carbon atoms), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), a hydroxy group or a phosphoamide group (preferably having 1 to 40 carbon atoms).
- the group represented by A preferably has at least one of a non-diffusible group and a group for promoting silver halide adsorption.
- the non-diffusible group is preferably a ballast group which is conventionally used in immobile photographic additives such as couplers, and the ballast group includes an alkyl, alkenyl, alkinyl or alkoxy group having not less than 8 carbon atoms or a phenyl, phenoxy or alkylphenoxy group, which is relatively inactive to photographic properties.
- the group for promoting silver halide adsorption includes a thiourea, thiourethane, mercapto, thioether, thion, heterocyclic, thioamidoheterocyclic or mercaptoheterocyclic group or an adsorption group described in Japanese Patent O.P.I. Publication No. 64-90439/1989.
- the example of B includes an acyl group (for example, formyl, acetyl, propionyl, trifluoroacetyl, methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl), an alkylsulfonyl group (for example, methanesulfonyl, chloroethanesulfonyl), an arylsulfonyl group (for example, benzenesulfonyl), an alkylsulfinyl group (for example, methanesulfinyl), an arylsulfinyl group (for example, benzenesulfinyl), a carbamoyl group (for example, methylcarbamoyl, phenylcarbamoyl), an alkoxycarbonyl group (for example, methoxycarbon
- B is especially preferably an acyl group or an oxalyl group.
- a 1 and A 2 represent both hydrogen atoms or one of A 1 and A 2 represents a hydrogen atom and the other represents an acyl group (acetyl, trifluoroacetyl, benzoyl), a sulfonyl group (methanesulfonyl, toluenesulfonyl) or an oxalyl group (ethoxalyl).
- acyl group acetyl, trifluoroacetyl, benzoyl
- a sulfonyl group methanesulfonyl, toluenesulfonyl
- oxalyl group ethoxalyl
- the compound represented by the following Formula (3) is especially preferable: wherein R 4 represents an aryl group or a heterocyclic group, R 5 represents group or -OR 8 group wherein R 6 and R 7 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a heterocyclic group, an amino group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocyclicoxy group, provided that R 6 and R 7 may form a ring together with a nitrogen atom, R 8 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group or a heterocyclic group, and A 1 and A 2 are the same as A 1 and A 2 of Formula (2), respectively.
- the aryl group represented by R 4 is preferably a single or condensed ring group, for example, a benzene ring group or a naphthalene ring group.
- the heterocyclic group represented by R 4 is preferably a single or condensed ring group containing a 5- or 6-membered heterocycle having one hetero atom selected from a nitrogen, sulfur and oxygen atom, such as a pyridine ring, a quinoline ring, a pyrimidine ring, a thiophene ring, a furan ring, a thiazole ring or a benzothiazole ring.
- R 4 is preferably a substituted or unsubstituted aryl group.
- the substituent is the same as that of A in Formula (2).
- R 4 is preferably a group having at least one sulfo group when a developer having pH of not more than 11.2 is used for high contrast.
- a 1 and A 2 are the same as A 1 and A 2 of Formula (2), respectively, and are most preferably simultaneously hydrogen atoms.
- R 6 and R 7 independently represent a hydrogen atom, an alkyl group (methyl, ethyl or benzyl), an alkenyl group (allyl, butenyl), an alkinyl group (propagyl, butinyl), an aryl group phenyl, naphthyl), a heterocyclic group (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl, quinolidinyl, N,N'-diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl), an amino group (amino, methylamino, dimethylamino, dibenzylamino), a hydroxy group, an alkoxy group (methoxy, ethoxy), an alkenyloxy group (allyloxy), an alkinyloxy group (propagyloxy), an aryloxy group (phenoxy) or a heterocyclic group (pyridyl), provided
- the synthetic method of a compound represented by Formula (2) is referred to in Japanese Patent O.P.I. Publication Nos. 62-180361, 62-178246, 63-234245, 63-234246, 64-90439, 2-37, 2-841, 2-947, 2-120736, 2-230233 and 3-125134, U.S.Patent Nos. 4,686,167, 4,988,604 and 4,994,365, European Patent Nos. 253,665 and 333,435.
- the content of the compound of the invention represented by Formula (2) is preferably 5 ⁇ 10 -7 to 5 ⁇ 10 -1 mol/mol of silver, and more preferably 5 ⁇ 10 -6 to 5 ⁇ 10 -2 mol/mol of silver.
- the compound represented by Formula (2) is contained in the silver halide emulsion layer or its adjacent hydrophilic colloid layers of a photographic light sensitive material.
- the nuclear promoting agent used in the invention includes a compound represented by the following Formula (4) or (5):
- R 41 , R 42 and R 43 independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkinyl group, an aryl group or a substituted aryl group, provided that R 41 , R 42 and R 43 may form a ring together and R 41 , R 42 and R 43 is not simultaneously hydrogen atoms.
- the preferable agent is an aliphatic tertiary amines. These compounds preferably have in the molecules an anti-diffusible group or a silver halide adsorption group.
- the compounds having anti-diffusible property have preferably a molecular weight not less than 100, and more preferably a molecular weight not less than 300.
- the preferable adsorption group includes a heterocyclic, mercapto, thioether, thion or thiourea group.
- Ar represents a substituted or unsubstituted aryl or aromatic heterocyclic group
- R represents an alkyl group, an alkenyl group, an alkinyl group or an aryl group, each of which may have a substituent.
- These compounds preferably have in the molecules an anti-diffusible group or a silver halide adsorption group.
- the compounds having anti-diffusible property have preferably a molecular weight not less than 120, and more preferably a molecular weight not less than 300.
- the nuclear promoting agent may be contained in the emulsion layer used in the invention or a layer adjacent thereto.
- the preferable examples of the substituents represented by R 1 through R 3 include an alkyl group (such as those of methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl and cyclohexyl), an amino group, an acylamino group (such as those of acetylamino), a hydroxyl group, an alkoxy group (such as those of methoxy, ethoxy, propoxy, butoxy and pentoxy), an acyloxy group (such as those of acetyloxy), a halogen atom (such as those of fluorine, chlorine and bromine), a carbamoyl group, an acylthio group (such as those of acetylthio), an alkoxycarbonyl group (
- the anion represented by the above-denoted X (-) includes, for example, a halogen ion such as a chloride ion, a bromide ion and an iodide ion, an acid residue of an inorganic acid such as nitric acid, sulfuric acid and perchloric acid, an acid residue of an organic acid such as sulfonic acid and carboxylic acid, an anionic type activator typically including a lower alkyl benzene sulfonic acid anion such as p-toluene sulfonic acid anion, a higher alkyl benzene sulfonic acid anion such as p-dodecyl benzene sulfonic acid anion, a higher alkyl sulfate anion such as lauryl sulfate anion, a boric acid type anion such as tetraphenyl boron, dialkyl sulfosuccinate anion such
- tetrazolium compounds used in the invention can be easily prepared by methods described on Chemical Reviews 55, pages 335-483.
- the content of the tetrazolium compound of Formula (6) is lmg to 10g, and preferably 10mg to 2g per mole of silver halide contained in the light sensitive material used in the invention.
- tetrazolium compounds used in the invention can be used singly or in combination in an appropriate proportion of two or more kinds.
- the conventional developer can be used in the invention.
- the developing agent used in the invention include dihydroxy benzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone or 2,5-dimethylhydroquinone), 3-pyrazolidone (for example, 1-phenyl-3-pyrazolidone, l-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone or l-phenyl-5-methyl-3-pyrazolidone), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-p-aminophenol or 2,4-diaminophenol), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (for example, 1-(p-hydroxyphenyl)-3-amin
- the combination of 3-pyrazolidones with dihydroxy benzenes or the combination of aminophenols with dihydroxy benzenes is preferable.
- the amount used of the developing agent is 0.01 to 1.4 mol per liter of developer.
- the sulfites or metabisulfites as preservatives include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite.
- the amount used of the sulfite is not less than 0.25 mol per liter, and preferably not less than 0.4 mol per liter of developer.
- the developer optionally contains alkali agents (sodium hydroxide or potassium hydroxide), pH buffering agents (for example, carbonates, phosphates, borates, boric acid, acetic acid, citric acid or alkanol amines), auxiliary solubility agents (for example, polyethylene glycols or salts thereof or alkanol amines), sensitizing agents (for example, non-ionic surfactant including polyoxy ethylenes or quaternary ammonium salts), surfactants, anti-foggants (for example, halides such as potassium bromide and sodium bromide, nitro benzindazole, nitro benzimidazole, benzotriazoles, benzothiazoles, tetrazoles or thiazoles), chelating agents (for example, ethylenediaminetetraacetic acid or an alkali metal salt thereof, nitrilotriacetic acid salts or polyphosphoric acid salts), hardeners (for example, sodium hydroxide
- the conventional fixer can be used in the invention.
- the fixer is usually an aqueous solution comprised of a fixing agent and other additives, and has a pH of 3.8 to 5.8.
- a fixing agent thiosulfates such as sodium thiosulfate, potassium thiosulfate or ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate or ammonium thiocyanate, or organic sulfur compounds capable of producing soluble stable silver complexes can be used.
- fixer can be added water soluble aluminum salts acting as a hardener such as aluminium chloride, aluminium sulfate and potash alum.
- preservatives such as sulfites or metabisulfites, pH buffering agents (for example, acetic acid), pH regulators (for example, sulfuric acid) or chelating agents capable of softening hard water.
- the light-sensitive material in the invention shows excellent properties in a rapid processing using an automatic developing apparatus wherein the total processing time is 15 to 60 seconds.
- the developing and fixing temperatures are independently 25°C to 50°C, and preferably 30°C to 40°C, and the developing and fixing times are independently not more than 25 seconds, and preferably 4 to 15 seconds.
- the total processing time is a total time taken from the entry of the leading edge of a film in the apparatus to the delivery of the leading edge out of the drying zone of the apparatus. The film is conveyed through the developing tank, the cross-over, the fixing tank, the cross-over, the washing tank, the cross-over and the drying zone in the automatic developing apparatus.
- a silver nitrate solution and a sodium chloride and potassium bromide solution prepared to contain 8 ⁇ 10 -5 mol/mol of silver of a rhodium hexachloride complex salt were added to a gelatin solution in a double-jet precipitation method, controlling the adding speed.
- the resulting solution was desalted and a monodisperse, cubic silver bromochloride emulsion having a silver bromide content of 1 mol% and a particle diameter of 0.13 ⁇ m was obtained.
- the resulting emulsion was sulfur-sensitized with the conventional method and added with 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene as a stabilizing agent. Then, a silver halide emulsion coating solution of the following Prescription 1 was prepared.
- a silver halide emulsion protective layer coating solution of the following Prescription 2 a backing layer coating solution of the following Prescription 3 and a bacing protective layer coating solution of the following Prescription 4 were prepared. The compositions will be shown below.
- Prescription 1 (a silver halide emulsion layer composition)
- Compound (a) 1mg/m 2 NaOH (0.5N) an amount necessary to adjust to pH 5.6
- Exemplified compound 6-6 Saponin (20% aqueous solution) 0.5 ml/m 2
- Sodium dodecylbenzenesulfonate 20 mg/m 2 5-Methylbenzotriazole 10 mg/m 2
- Compound (d) 2 mg/m 2
- Compound (e) 10 mg/m 2
- Compound (f) 6 mg/m 2 Latex Lx-1 0.5 g/m 2 Styrene-maleic acid copolymer (thickner) 90 mg/m 2
- a polyethylene terephthalate support subbed on an emulsion side as shown in Japanese Patent O.P.I. Publication No. 59-19941 was corona-discharged in strength of 10(w/m2 ⁇ min).
- the emulsion side of the support were simultaneously coated at 35°C the emulsion layer of Prescription 1 and the emulsion protective layer of Prescription 2 in order according to a slide hopper method adding the above hardening solution and was set at a setting zone (5°C). Thereafter, the resulting material was coated on the side opposite the emulsion side with the backing layer of Prescription 3 and the backing protective layer of Prescription 4 in order according to a slide hopper method and was set with a cold air. The material was sufficiently set through the setting zones and both surface of the material was further dried at a drying zone under the following drying conditions.
- the transport before rolling after the backing layer side was coated was carried out using a roller and transport other than that was carried out without contact.
- the coating speed was 100m/min.
- the coated material after set was dried with a 30°C air to have a H 2 O/gelatin ratio of 800%, and then dried with a 30°C and 30%RH air to have a H 2 O/gelatin ratio of 200%.
- the resulting material was dried for 1 minute with a 48°C and 2%RH air 30 seconds after the surface temperature reached 34°C (judged as completion of drying).
- the time necessary to have a H 2 O/gelatin ratio of 800% was 50 seconds
- the time necessary to have a H 2 O/gelatin ratio of 800-200% was 35 seconds
- the time from the H 2 O/gelatin ratio of 800% till the completion of drying was 5 seconds.
- the thus obtained light sensitive material was rolled, cut at 23°C and 40%RH and tightly packaged with card board in a barrier package subjected for 3 hours to 23°C, 40%RH humidity conditioning.
- the barrier package was in advance subjected to humidity conditioning of 40°C and 10%RH for 8 hours and further 23°C and 30%RH for 2 hours.
- Samples were prepared in the same manner as above, except that compounds of Formula (1) shown in Table 1 were added in an amount as shown in Table 1. Thus, 25 samples were prepared.
- the samples above obtained had a silver coating amount of 4.0g/m 2 and a gelatin content of the emulsion layer of 2.0g/m 2 .
- the gelatin content refers to the total gelatin content of the silver halide emulsion layer and the protective emulsion layer.
- a silver bromoiodochloride emulsion containing 70 mol% of silver chloride, 0.2 mol% of silver iodide and silver bromide was prepared in a double-jet precipitation method.
- K 3 RhBr 6 was added in an amount of 8.1 ⁇ 10 -8 mol/mol of silver.
- the resulting emulsion was proved to be an emulsion comprising cubic monodisperse grains having an average particle diameter of 0.20 ⁇ m (with a variation coefficient of 9%).
- the emulsion was desalted with denatured gelatin disclosed in Japanese Patent O.P.I. Publication No.
- 2-280139 one in which an amino group in gelatin is substituted with a phenylcarbamyl group, for example, Exemplified compound G-8 in Japanese Patent O.P.I. Publication No. 2-280139).
- the resulting EAg after the desalting was 190mv at 50°C.
- the resulting emulsion was adjusted to be pH 5.58 and EAg 123mv, and the temperature thereof was elevated to 60°C.
- To the emulsion was added 2.2 ⁇ 10 -5 mol/mol of silver of chloroauric acid and the mixture was stirred for 2 minutes.
- To the mixture emulsion was added 2.9 ⁇ 10 -6 mol/mol of silver of S 8 and the mixture was chemically ripened for 78 minutes.
- Example 2 In the same manner as in Example 1 a 100 ⁇ m thick polyethylene terephthalate film was coated on the subbing layer on one side with the silver halide emulsion of the following prescription 1 containing silver halide emulsion A to give a silver content of 3.3g/m 2 and a gelatin content of 1.6g/m 2 . As a protective layer the composition of the following prescription 2 was coated on the emulsion layer to give a gelatin content of 1.0g/m 2 .
- the backing layer composition of the following prescription 3 was coated on the subbing layer on the other side to give a gelatin content of 2.7g/m 2 and the backing protective layer composition of the following prescription 4 was coated on the backing layer to give a gelatin content of 1g/m 2 and dried in the same manner as in Example 1.
- Samples were prepared in the same manner as above, except that compounds of Formula (1) shown in Table 2 were added in an amount as shown in Table 2. Thus, 25 samples were prepared.
- compositions A and B were dissolved in 500 ml and water was added to make 1 litre.
- the resulting solution was adjusted with acetic acid to be pH 4.8.
- the 610 ⁇ 590 mm light sensitive material 1 was processed at a rate of 200 sheets per day for successive 10 days with the above developer and fixer using an automatic developing machine GR-26SR (produced by Konica Corporation).
- the light sensitive material was processed at a rate of unexposed one 4:exposed one 1.
- the processing was carried out for a replenishing amount of developer replenisher of 50, 100, 160 and 200ml/m 2 .
- the developer replenisher was the same as the above developer.
- the processing condition will be shown below. Processing condition (light sensitive material 1) (Processing step) (Temperature) (Time) Developing 35°C 15 seconds Fixing 36°C 12 seconds Washing room temp. 10 seconds Drying 50°C 10 seconds
- the silver concentration of the resulting developer was measured.
- the light sensitive material 1 was exposed to a UV light through a contact screen having a 50 % dot, developed the exposed material, and evaluated using a magnifier for dot quality according to the following criteria. 5 excellent 4 good 3 fair 2 poor 1 very poor
- the present invention makes it possible in the rapid processing condition to reduce a replenishing amount of developer replenisher and to markedly prevent silver staining due to less silver dissolved.
- Light sensitive material 2 was running processed in the same manner as in Example 1, except that the light sensitive material was processed at a rate of unexposed one 1:exposed one 1 and under the processing condition as shown below.
- Processing condition light sensitive material 2
- Processing step (Temperature)
- Tempoture (Time) Developing 35°C 30 seconds Fixing 33°C 20 seconds Washing room temp. 20 seconds Drying 40°C 40 seconds
- the silver concentration of the resulting developer was measured.
- the processed light sensitive materials were evaluated for black spots and dot quality.
- the light sensitive material 2 was exposed to a He-Ne light for 10-6 seconds through a contact screen having a 50 % dot, developed the exposed material, and evaluated using a magnifier for dot quality according to the following criteria. 5 excellent 4 good 3 fair 2 poor 1 very poor
- the present invention makes it possible to markedly prevent silver staining due to less silver dissolved even when a light sensitive material was processed with a reduced replenishing amount (not more than 200ml/m 2 ) of developer replenisher.
- inventive samples gives excellent dot quality and prevention of black spots compared with comparative samples.
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Description
R21 | R22 | R23 | |
B-1 | H | H | SH |
B-2 | H | SH | H |
B-3 | CH3 | H | SH |
B-4 | OH | H | SH |
B-5 | H | NH2 | SH |
B-6 | Cl | SH | H |
B-7 | COOH | H | SH |
R21 | R22 | R23 | R24 | |
B-8 | H | H | H | SH |
B-9 | Cl | H | H | SH |
B-10 | SH | H | H | H |
B-11 | nC5H11 | H | H | SH |
B-12 | OH | H | H | SH |
B-13 | H | H | OH | SH |
B-14 | SH | H | SH | H |
R21 | R22 | |
B-15 | SH | H |
B-16 | SH | SH |
B-17 | SH | COOH |
B-18 | SH | SO3H |
B-19 | SH | OH |
R21 | R22 | |
B-20 | SH | H |
B-21 | SH | SH |
B-22 | SH | COOH |
B-23 | SH | SO3H |
B-24 | SH | OH |
R21 | R22 | R23 | R24 | |
B-25 | H | H | H | SH |
B-26 | H | H | SH | SH |
B-27 | OH | H | H | SH |
B-28 | H | C5H11 | H | SH |
B-29 | SH | COOH | H | H |
B-30 | H | H | SO3H | SH |
R21 | R22 | R23 | |
B-31 | H | H | SH |
B-32 | H | SH | OH |
B-33 | CH3 | H | SH |
B-34 | OH | H | SH |
B-35 | H | OH | SH |
B-36 | Cl | SH | H |
B-37 | COOH | H | SH |
B-38 | H | NH2 | SH |
B-39 | SH | OH | H |
Examplified compounds represented by Formula (g) | ||||
R31 | R32 | R33 | R34 | |
g-1 | -SH | H | H | H |
g-2 | -SH | -OH | H | H |
g-3 | -SH | H | -OH | H |
g-4 | -SH | -CH3 | -OH | H |
g-5 | -SH | -NH2 | H | H |
g-6 | -SH | H | H | -NH2 |
g-7 | -SH | H | -CH3 | -CH3 |
g-8 | -SH | H | H | -SH |
g-9 | -SH | -OH | H | -SH |
g-10 | -SH | H | H | -COOH |
g-11 | H | -SH | H | H |
g-12 | -SH | -SH | H | H |
g-13 | H | -SH | -OH | H |
g-14 | H | -SH | -NH2 | H |
g-15 | H | -SH | -OH | -CH3 |
g-16 | H | -SH | -NH2 | -C2H5 |
g-17 | H | -SH | H | -CH3 |
g-18 | H | -SH | H | -OH |
g-19 | H | -SH | H | -COOH |
g-20 | H | -SH | H | -SO3H |
g-21 | H | H | -SH | H |
g-22 | -OH | H | -SH | H |
g-23 | -OH | -CH3 | -SH | H |
g-24 | -NH2 | H | -SH | H |
g-25 | -SH | H | -SH | H |
g-26 | H | H | H | -SH |
g-27 | H | -OH | H | -SH |
g-28 | -OH | H | H | -SH |
g-29 | -NH2 | H | H | -SH |
g-30 | H | -NH2 | H | -SH |
g-31 | H | -NH2 | -CH3 | -SH |
g-32 | -SH | H | H | -SH |
g-33 | -SH | -CH3 | H | -SH |
g-34 | H | -OCH3 | H | -SH |
g-35 | -SH | -SH | H | -SH |
g-36 | H | -CH3 | -CH3 | -SH |
Examplified compounds represented by Formula (h) | ||||
R31 | R32 | R33 | R34 | |
h-1 | H | H | -NH2 | -SH |
h-2 | H | -CH3 | -NH2 | -SH |
h-3 | H | H | -SH | -SH |
h-4 | -OH | H | -SH | -SH |
h-5 | H | H | -COOH | -SH |
h-6 | H | H | H | -SH |
h-7 | -OH | H | H | -SH |
h-8 | H | -OH | H | -SH |
h-9 | -CH3 | -OH | H | -SH |
h-10 | -NH2 | H | H | -SH |
h-11 | -OH | H | -SH | H |
h-12 | -NH2 | H | -SH | H |
h-13 | -OH | -CH3 | -SH | H |
h-14 | -NH2 | -C2H5 | -SH | H |
h-15 | H | -CH3 | -SH | H |
h-16 | H | -OH | -SH | H |
h-17 | H | H | -SH | H |
h-18 | -OH | H | -SH | -CH3 |
h-19 | -OH | -CH3 | -SH | H |
h-20 | -NH2 | H | -SH | H |
h-21 | -SH | H | -SH | H |
h-22 | H | -SH | H | -OH |
h-23 | H | -SH | -OH | -NH2 |
h-24 | H | -SH | -NH2 | H |
h-25 | H | -SH | -COOH | H |
h-26 | H | -SH | H | H |
h-27 | -OCH3 | -SH | H | H |
h-28 | H | -SH | H | -SO3H |
h-29 | -SH | H | H | H |
h-30 | -SH | -OH | H | H |
h-31 | -SH | H | H | -NH2 |
h-32 | -SH | -CH3 | H | H |
(a) | Ethyl acrylate | 5.0 kg |
(b) | Methylmethacrylate | 1.4 kg 35°C |
(c) | Styrene | 3.0 kg |
(d) | Acrylamide-2-methylpropane sulfonic acid sodium salt | 0.6 g |
(a) | n-Butyl acrylate | 4.51 kg |
(b) | Styrene | 5.49 kg |
(c) | Acrylic acid | 0.1 kg |
Prescription 1 (a silver halide emulsion layer composition) | |
Compound (a) | 1mg/m2 |
NaOH (0.5N) | an amount necessary to adjust to pH 5.6 |
Compound (b) Tetrazolium compound | 40mg/m2 |
Exemplified compound 6-6 | |
Saponin (20% aqueous solution) | 0.5 ml/m2 |
Sodium dodecylbenzenesulfonate | 20 mg/m2 |
5-Methylbenzotriazole | 10 mg/m2 |
Compound (d) | 2 mg/m2 |
Compound (e) | 10 mg/m2 |
Compound (f) | 6 mg/m2 |
Latex Lx-1 | 0.5 g/m2 |
Styrene-maleic acid copolymer (thickner) | 90 mg/m2 |
Prescription 2 (a silver halide emulsion layer protective composition) | |
Gelatin | 0.5 g/m2 |
Compound (g) (1 % aqueous solution) | 25 ml/m2 |
Compound (h) | 120 mg/m2 |
Monodisperse spherical silica (8µm) | 20 mg/m2 |
Monodisperse spherical silica (3µm) | 10 mg/m2 |
Compound (i) | 100 mg/m2 |
Citric acid an amount necessary to adjust | to pH 6.0 |
Latex Lx-2 | 0.5 g/m2 |
Prescription 3 (a backing layer composition) | |
Gelatin | 1.0 g/m2 |
Compound (j) | 100 mg/m2 |
Compound (k) | 18 mg/m2 |
Compound (ℓ) | 100 mg/m2 |
Saponin (20% aqueous solution) | 0.6 ml/m2 |
Latex (m) | 300 mg/m2 |
5-Nitroindazole | 20 mg/m2 |
Styrene-maleic acid copolymer (thickner) | 45 mg/m2 |
Glyoxal | 4 mg/m2 |
Compound (o) | 100 mg/m2 |
Compound of Formula (1) | Shown in Table 1 |
Prescription 4 (a backing protective layer composition) | |
Gelatin | 0.5 g/m2 |
Compound (g) (1%) | 2 ml/m2 |
Spherical polymethylmethacrylate (4µm) | 25 mg/m2 |
Sodium chloride | 70 mg/m2 |
Glyoxal | 22 mg/m2 |
Compound (n) | 100 mg/m2 |
Prescription 4(Backing protective layer composition) | |
Matting agent: monodisperse polymethylmethacrylate having an average particle size of 5.0µm | 50 mg/m2 |
Sodium di-(2-ethylhexyl) sulfosuccinate | 10 mg/m2 |
(Prescription of Developer) | |
Sodium sulfite | 55 g/litre |
Sodium carbonate | 40 g/liter |
Hydroquinone | 24 g/litre |
4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone (Dimeson S) | 0.9 g/litre |
Potassium bromide | 5 g/litre |
5-methyl-benzotriazole | 0.13 g/litre |
Boric acid | 2.2 g/liter |
Diethyleneglycol | 40 g/litre |
2-mercaptohypoxanthine | 60 mg/litre |
(Prescription of Fixer) | |
Composition A | |
Ammonium thiosulfate(72.5%W/V solution) | 240 ml |
Sodium sulfite | 17 g |
Sodium acetate trihydrate | 6.5 g |
Boric acid | 6.0 g |
Citric acid bihydrate | 2.0 g |
Composition B | |
Pure water (deionized water) | 17 ml |
Surfuric acid (aq. 50%W/V solution) | 4.7 g |
Aluminum sulfate (an aqueous 8.1 %W/V solution converted into an Al2O3 content) | 26.5 g |
Processing condition (light sensitive material 1) | ||
(Processing step) | (Temperature) | (Time) |
Developing | 35°C | 15 seconds |
Fixing | 36°C | 12 seconds |
Washing | room temp. | 10 seconds |
Drying | 50°C | 10 seconds |
5 | excellent |
4 | good |
3 | fair |
2 | poor |
1 | very poor |
Light sensitive material 1 Sample No. | Compound of Formula 1 | Content (mg/ m2) | Replenishing amount of developer replenisher (ml) | Remarks | |||||||
50 | 100 | 160 | 200 | ||||||||
a | b | a | b | a | b | a | b | ||||
1-1 | None | - | 34.5 | 3 | 28.7 | 3 | 23.1 | 3 | 18.7 | 3 | Comp. |
1-2 | [A-4] | 3 | 33.3 | 3 | 27.4 | 3 | 22.5 | 3 | 18.1 | 3 | Comp. |
5 | 5.6 | 4 | 5.2 | 4 | 4.9 | 4 | 4.7 | 4 | Inv. | ||
10 | 4.5 | 4 | 4.3 | 4 | 4.1 | 4 | 4.0 | 5 | Inv. | ||
100 | 1.3 | 4 | 1.3 | 5 | 1.2 | 5 | 1.2 | 5 | Inv. | ||
200 | 0.6 | 4 | 0.5 | 5 | 0.5 | 5 | 0.4 | 5 | Inv. | ||
210 | 0.6 | 2 | 0.6 | 3 | 0.6 | 3 | 0.5 | 3 | Comp. | ||
1-3 | [B-35] | 3 | 32.9 | 3 | 27.3 | 3 | 21.7 | 3 | 17.8 | 3 | Comp. |
5 | 5.3 | 4 | 5.0 | 4 | 4.8 | 4 | 4.5 | 4 | Inv. | ||
10 | 4.4 | 4 | 4.2 | 4 | 4.1 | 5 | 3.9 | 5 | Inv. | ||
100 | 1.3 | 4 | 1.2 | 5 | 1.2 | 5 | 1.1 | 5 | Inv. | ||
200 | 0.5 | 4 | 0.5 | 5 | 0.4 | 5 | 0.4 | 5 | Inv. | ||
210 | 0.6 | 2 | 0.6 | 3 | 0.5 | 3 | 0.5 | 3 | Comp. | ||
1-4 | [g-27] | 3 | 32.5 | 3 | 26.5 | 3 | 19.8 | 3 | 16.1 | 3 | Comp. |
5 | 4.4 | 4 | 4.2 | 4 | 4.0 | 5 | 3.7 | 5 | Inv. | ||
10 | 3.7 | 4 | 3.5 | 4 | 3.0 | 5 | 2.9 | 5 | Inv. | ||
100 | 1.3 | 4 | 1.2 | 5 | 1.2 | 5 | 1.0 | 5 | Inv. | ||
200 | 0.5 | 4 | 0.5 | 5 | 0.4 | 5 | 0.4 | 5 | Inv. | ||
210 | 0.7 | 2 | 0.6 | 3 | 0.6 | 3 | 0.5 | 3 | Comp. | ||
1-5 | [g-13] | 3 | 32.6 | 3 | 26.9 | 3 | 20.8 | 3 | 16.8 | 3 | Comp. |
5 | 4.6 | 4 | 4.5 | 4 | 4.3 | 5 | 3.9 | 5 | Inv. | ||
10 | 3.8 | 4 | 3.5 | 4 | 3.4 | 5 | 3.3 | 5 | Inv. | ||
100 | 1.4 | 4 | 1.4 | 5 | 1.3 | 5 | 1.1 | 5 | Inv. | ||
200 | 0.5 | 4 | 0.5 | 5 | 0.4 | 5 | 0.4 | 5 | Inv. | ||
210 | 0.6 | 2 | 0.6 | 3 | 0.6 | 3 | 0.5 | 3 | Comp. | ||
a: Silver content (ppm) in the developer | |||||||||||
b: Dot quality |
Processing condition (light sensitive material 2) | ||
(Processing step) | (Temperature) | (Time) |
Developing | 35°C | 30 seconds |
Fixing | 33°C | 20 seconds |
Washing | room temp. | 20 seconds |
Drying | 40°C | 40 seconds |
5 | excellent |
4 | good |
3 | fair |
2 | poor |
1 | very poor |
5 | excellent |
4 | good |
3 | fair |
2 | poor |
1 | very poor |
Light sensitive material 1 Sample No. | Compound of Formula 1 | Content (mg/ m2) | Replenishing amount of developer replenisher (ml) | Remarks | |||||||||||
50 | 100 | 160 | 200 | ||||||||||||
a | b | c | a | b | c | a | b | c | a | b | c | ||||
2-1 | None | - | 40.7 | 2 | 1 | 35.4 | 2 | 1 | 29.4 | 2 | 1 | 24.7 | 3 | 2 | Comp. |
2-2 | [A-4] | 3 | 39.1 | 2 | 1 | 33.8 | 2 | 1 | 28.4 | 2 | 1 | 23.1 | 3 | 2 | Comp. |
5 | 7.5 | 3 | 3 | 7.1 | 3 | 4 | 6.5 | 4 | 4 | 6.3 | 4 | 4 | Inv. | ||
10 | 6.0 | 4 | 4 | 5.4 | 4 | 4 | 5.1 | 5 | 4 | 5.0 | 5 | 5 | Inv. | ||
100 | 3.8 | 4 | 4 | 3.6 | 5 | 4 | 3.3 | 5 | 5 | 2.9 | 5 | 5 | Inv. | ||
200 | 1.9 | 5 | 5 | 1.9 | 5 | 5 | 1.8 | 5 | 5 | 1.7 | 5 | 5 | Inv. | ||
210 | 2.4 | 2 | 2 | 2.5 | 2 | 2 | 2.4 | 2 | 2 | 3.0 | 2 | 2 | Comp. | ||
2-3 | [B-35] | 3 | 38.7 | 2 | 1 | 33.4 | 2 | 1 | 127.9 | 2 | 1 | 22.8 | 2 | 2 | Comp. |
5 | 7.3 | 3 | 3 | 7.0 | 3 | 4 | 6.6 | 4 | 4 | 6.1 | 4 | 4 | Inv. | ||
10 | 5.2 | 4 | 4 | 4.7 | 4 | 4 | 4.7 | 5 | 4 | 4.5 | 5 | 5 | Inv. | ||
100 | 3.5 | 4 | 4 | 3.2 | 5 | 4 | 2.9 | 5 | 5 | 2.6 | 5 | 5 | Inv. | ||
200 | 1.8 | 5 | 5 | 1.7 | 5 | 5 | 1.5 | 5 | 5 | 1.5 | 5 | 5 | Inv. | ||
210 | 2.2 | 2 | 2 | 2.3 | 2 | 2 | 2.2 | 2 | 2 | 2.1 | 2 | 2 | Comp. | ||
2-4 | [g-27] | 3 | 36.5 | 2 | 1 | 31.4 | 2 | 1 | 25.7 | 2 | 1 | 20.5 | 2 | 2 | Comp. |
5 | 6.9 | 3 | 3 | 6.5 | 3 | 4 | 5.9 | 4 | 4 | 5.3 | 4 | 4 | Inv. | ||
10 | 4.8 | 4 | 4 | 4.4 | 4 | 4 | 4.3 | 5 | 5 | 4.0 | 5 | 5 | Inv. | ||
100 | 2.5 | 4 | 4 | 2.4 | 5 | 4 | 2.4 | 5 | 5 | 2.3 | 5 | 5 | Inv. | ||
200 | 1.4 | 5 | 5 | 1.4 | 5 | 5 | 1.3 | 5 | 5 | 1.3 | 5 | 5 | Inv. | ||
210 | 1.9 | 2 | 2 | 2.0 | 2 | 2 | 2.0 | 2 | 2 | 2.0 | 2 | 2 | Comp. | ||
2-5 | [g-13] | 3 | 37.8 | 2 | 1 | 32.5 | 2 | 1 | 26.2 | 2 | 1 | 21.6 | 2 | 2 | Comp. |
5 | 7.4 | 3 | 3 | 6.8 | 3 | 4 | 6.0 | 4 | 4 | 5.6 | 4 | 4 | Inv. | ||
10 | 5.2 | 4 | 4 | 4.8 | 4 | 4 | 4.7 | 5 | 5 | 4.3 | 5 | 5 | Inv. | ||
100 | 2.7 | 4 | 4 | 2.6 | 5 | 4 | 2.6 | 5 | 5 | 2.4 | 5 | 5 | Inv. | ||
200 | 1.6 | 5 | 5 | 1.6 | 5 | 5 | 1.5 | 5 | 5 | 1.4 | 5 | 5 | Inv. | ||
210 | 2.5 | 2 | 2 | 2.5 | 2 | 2 | 3.0 | 2 | 2 | 2.0 | 2 | 2 | Comp. | ||
a: Silver content (ppm) in the developer | |||||||||||||||
b: Dot quality | |||||||||||||||
c: Black spots |
Claims (7)
- A method of processing a photographic light-sensitive material comprising a support, a silver halide emulsion layer provided thereon and a backing layer on the support opposite the emulsion layer, comprising the steps of:
exposing the material;
developing the exposed material with developer, said developer being replenished with developer replenisher in an amount of not more than 200 ml per m2 of the material,; and
fixing the developed material,
wherein the backing layer contains in an amount of 5 to 200 mg/m2 a compound represented by the following Formula (1): wherein Z represents a nitrogen-containing heterocyclic ring; and M represents a hydrogen atom, an alkali metal atom, an alkali earth metal atom or an ammonium ion. - The method of claim 1, wherein the compound represented by Formula (1) is selected from the group consisting of compounds represented by the following Formulas (A), (B) and (C): wherein R1 and R2 independently represent an alkyl, aryl, aralkyl, hydroxy, carboxy, sulfo, phosphono, amino, nitro, cyano, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfamoyl or alkoxy group or a halogen atom, provided that R1 and R2 may combine to form a ring, wherein Z21 and Y21 independently represent an atomic group necessary to form an unsaturated 5- or 6-membered ring, provided that three or more nitrogen atoms are contained in Z21 and Y21 and one of Z21 and Y21 has a mercapto group as a substituent, wherein Z31 and Y31 independently represent an atomic group necessary to form an unsaturated 5- or 6-membered ring, provided that three or more nitrogen atoms are contained in Z31 and Y31 and one of Z31 and Y31 has a mercapto group as a substituent.
- The method of claim 1, wherein the backing layer contains said compound in an amount of 7 to 150 mg/m2.
- The method of claim 1, wherein said developer is replenished with developer replenisher in an amount of 50 to 160 ml per m2 of the material.
- The method of claim 1, wherein the total processing time is 15 to 60 seconds.
- The method of claim 1, wherein said silver halide emulsion layer comprises a hydrazine compound represented by the following Formula (2): wherein A represents an aliphatic group, or cyclic alkyl group having 1 to 20 carbon atoms an aryl group or a heterocyclic group; B represents an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, an oxalyl group or a heterocyclic group, provided that B may form, together with A2 and a nitrogen atom, -N=C(R9)(R10) in which R9 represents an alkyl group, an aryl group or a heterocyclic group and R10 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; and A1 and A2 both represent hydrogen atoms or one of A1 and A2 represents a hydrogen atom and the other represents an acyl group, a sulfonyl group or an oxalyl group.
- The method of claim 6, wherein the content of said hydrazine compound is 5 × 10-7 to 5 × 10-1 mol/mol of silver.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6971894 | 1994-04-07 | ||
JP6069718A JPH07281365A (en) | 1994-04-07 | 1994-04-07 | Method for processing silver halide photographic sensitive material |
JP69718/94 | 1994-04-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0676667A1 EP0676667A1 (en) | 1995-10-11 |
EP0676667B1 true EP0676667B1 (en) | 2000-01-12 |
Family
ID=13410900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95105017A Expired - Lifetime EP0676667B1 (en) | 1994-04-07 | 1995-04-04 | Method of processing photographic light-sensitive material |
Country Status (4)
Country | Link |
---|---|
US (1) | US5591567A (en) |
EP (1) | EP0676667B1 (en) |
JP (1) | JPH07281365A (en) |
DE (1) | DE69514399T2 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3555788B2 (en) * | 1995-06-21 | 2004-08-18 | 富士写真フイルム株式会社 | Developing method of silver halide photographic material |
JP3523416B2 (en) * | 1996-03-05 | 2004-04-26 | 富士写真フイルム株式会社 | Liquid developer for silver halide photographic material and method for developing silver halide photographic material |
JP2002189271A (en) | 2000-12-21 | 2002-07-05 | Fuji Photo Film Co Ltd | Silver halide photosensitive material and processing method for the same |
US8343977B2 (en) | 2009-12-30 | 2013-01-01 | Arqule, Inc. | Substituted triazolo-pyrimidine compounds |
NZ702571A (en) | 2012-06-29 | 2017-02-24 | Pfizer | 4-(substituted-amino)-7h-pyrrolo[2,3-d]pyrimidines as lrrk2 inhibitors |
JP6487921B2 (en) | 2013-12-17 | 2019-03-20 | ファイザー・インク | Novel 3,4-disubstituted-1H-pyrrolo [2,3-b] pyridines and 4,5-disubstituted-7H-pyrrolo [2,3-c] pyridazines as LRRK2 inhibitors |
CN108137586B (en) | 2015-09-14 | 2021-04-13 | 辉瑞大药厂 | Novel imidazo [4,5-c ] quinoline and imidazo [4,5-c ] [1,5] naphthyridine derivatives as LRRK2 inhibitors |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1522369A1 (en) * | 1966-04-19 | 1969-08-14 | Agfa Gevaert Ag | Process for producing photographic images by the silver salt diffusion process |
JPH0833603B2 (en) * | 1985-04-18 | 1996-03-29 | 富士写真フイルム株式会社 | Silver halide photographic light-sensitive material and ultrahigh contrast negative image forming method using the same |
JPH0736076B2 (en) * | 1986-03-24 | 1995-04-19 | 富士写真フイルム株式会社 | Silver halide photographic light-sensitive material and image forming method using the same |
JPS63142352A (en) * | 1986-12-04 | 1988-06-14 | Konica Corp | Silver halide color photographic sensitive material ensuring improved graininess and sharpness |
JPH01131545A (en) * | 1987-08-17 | 1989-05-24 | Konica Corp | Silver halide photographic sensitive material and its processing |
EP0327066A3 (en) * | 1988-02-01 | 1990-06-27 | Fuji Photo Film Co., Ltd. | Direct positive photographic material |
JPH01319031A (en) * | 1988-06-20 | 1989-12-25 | Konica Corp | Silver halide black and white photographic sensitive material |
JPH02150840A (en) * | 1988-12-02 | 1990-06-11 | Konica Corp | Silver halide color photographic sensitive material having excellent rapid processing adaptability and preservable property |
JPH0365950A (en) * | 1989-08-04 | 1991-03-20 | Konica Corp | Method for processing silver halide photographic sensitive material |
JPH03287252A (en) * | 1990-04-03 | 1991-12-17 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
JP2676426B2 (en) * | 1990-10-25 | 1997-11-17 | 富士写真フイルム株式会社 | Silver halide photographic material |
JP2873634B2 (en) * | 1991-04-11 | 1999-03-24 | コニカ株式会社 | Silver halide photographic material |
EP0529152B1 (en) * | 1991-08-13 | 1996-12-11 | Agfa-Gevaert N.V. | A new class of masked stabilizers in photographic materials or developing solutions |
EP0529526B1 (en) * | 1991-08-22 | 1999-05-06 | Fuji Photo Film Co., Ltd. | Developing solution for silver halide photographic material and method for processing silver halide photographic material by using the same |
JPH0772582A (en) * | 1993-03-18 | 1995-03-17 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material and treating method thereof |
JPH06308679A (en) * | 1993-04-27 | 1994-11-04 | Fuji Photo Film Co Ltd | Method for processing silver photographic sensitive material |
-
1994
- 1994-04-07 JP JP6069718A patent/JPH07281365A/en active Pending
-
1995
- 1995-03-29 US US08/412,750 patent/US5591567A/en not_active Expired - Fee Related
- 1995-04-04 EP EP95105017A patent/EP0676667B1/en not_active Expired - Lifetime
- 1995-04-04 DE DE69514399T patent/DE69514399T2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE69514399T2 (en) | 2000-06-08 |
JPH07281365A (en) | 1995-10-27 |
DE69514399D1 (en) | 2000-02-17 |
US5591567A (en) | 1997-01-07 |
EP0676667A1 (en) | 1995-10-11 |
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